Azodicarboxylic acid derivatives containing hindered amine moieties as polymer stabilizers

Abstract

New azodicarboxylic acid derivatives of formula I ##STR1## where R 1 is hydrogen, oxyl, hydroxyl, alkyl, allyl, benzyl, alkoxy or acyl, and X is --O-- or --NR-- where R is hydrogen or alkyl, are useful for the stabilization of polymers, particularly unsaturated elastomers, by being grafted thereon.

What is claimed is: 
     
       1. A compound which is an azo derivative of formula IV ##STR28## where R 1  is hydrogen, oxyl, hydroxyl, alkyl of 1 to 8 carbon atoms, alkyl of 2 to 4 carbon atoms substituted by one hydroxyl group, allyl, benzyl, benzyl substituted by one of two alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms or alkanoyl of 1 to 8 carbon atoms; X is --O-- or --NR 2  -- where R 2  is hydrogen, alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, alkyl of 2 to 4 carbon atoms substituted by one alkoxy group of 1 to 12 carbon atoms or a group of formula II ##STR29## in which R 1  is as defined above; and E is alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 14 carbon atoms or phenylalkyl of 7 to 22 carbon atoms, or   E is --CONHR 4 , --CSNHR 5 , --COR 6  COR 7 , --COR 8  CONHR 9 , --COR 10 , --COOR 11  or --SO 2  R 12 ,   in which R 4 , R 5 , R 7 , R 9 , R 10 , R 11  and R 12  are each independently of the other hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 14 carbon atoms or phenylalkyl of 7 to 22 carbon atoms; and   R 6  and R 8  are each independently of the other an alkylene of 1 to 12 carbons.   
     
     
       2. A stabilized polymer composition which comprises (a) a polymer, copolymer or polymer blend which contains in at least one polymer or polymer component significant ethylenic unsaturation, and   (b) an effective stabilizing amount of an asymmetrical azo derivative grafted to said polymer or polymer component, said derivative having before grafting the structure of formula IV ##STR30## where R 1  is hydrogen, oxyl, hydroxyl, alkyl of 1 to 8 carbon atoms, alkyl of 2 to 4 carbon atoms substituted by one hydroxyl group, allyl, benzyl, benzyl substituted by one of two alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms or alkanoyl of 1 to 8 carbon atoms;   X is --O-- or --NR 2  -- where R 2  is hydrogen, alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, alkyl of 2 to 4 carbon atoms substituted by one alkoxy group of 1 to 12 carbon atoms or a group of formula II ##STR31## in which R 1  is as defined above; and E is a alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 14 carbon atoms or phenylalkyl of 7 to 22 carbon atoms, or   E is --CONHR 4 , --CSNHR 5 , --COR 6  COR 7 , --COR 8  CONHR 9 , --COR 10 , --COOR 11  or --SO 2  R 12 ,   in which R 4 , R 5 , R 7 , R 9 , R 10 , R 11  and R 12  are each independently of the other hydrogen, alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aryl of 6 to 14 carbon atoms or phenylalkyl of 7 to 22 carbon atoms; and   R 6  and R 8  are each independently of the other an alkylene of 1 to 12 carbons.   
     
     
       3. A composition according to claim 2 wherein component (a) is a polymer, copolymer or polymer blend, having significant ethylenic unsaturation in at least one polymer or polymer component, selected from the group consisting of ABS, HIPS, emulsion SBR, PP/EPDM, PP/NBR, PP/NR, ABS/PC, ABS/nylon, ABS/PVC, ABS/polyester, ABS/SMA, ABS/polysulfone, ASA/PC, acetal/elastomer, polyester/elastomer, nylon/elastomer, PPO/NR, EPDM/NBR and EPDM/olefin. 
     
     
       4. A composition according to claim 3 wherein component (a) is ABS or ABS/PC. 
     
     
       5. A compound of formula IV according to claim 1, wherein E is an alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl or phenylalkyl of 7 to 14 carbon atoms. 
     
     
       6. A compound of formula IV according to claim 1, wherein E is alkyl of 1 to 10 carbon atoms, cyclohexyl, phenyl or phenylalkyl of 7 to 9 carbon atoms. 
     
     
       7. A compound of formula IV according to claim 1, wherein E is --CONHR 4  or --CSNHR 5  and R 4  and R 5  are each independently of the other alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl or phenylalkyl of 7 to 14 carbon atoms. 
     
     
       8. A compound of formula IV according to claim 1, wherein E is --CONHR 4  or --CSNHR 5  and R 4  and R 5  are each independently of the other alkyl of 1 to 10 carbon atoms, cyclohexyl, phenyl or phenylalkyl of 7 to 9 carbon atoms. 
     
     
       9. A compound of formula IV according to claim 1, wherein E is --COR 6  COR 7  or --COR 8  CONHR 9  and R 6  and R 8  are each independently of the other alkylene of 1 to 8 carbon atoms and R 7  and R 9  are each independently of the other alkyl of 1 to 8 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, aryl of 6 to 12 carbon atoms or phenylalkyl of 7 to 14 carbon atoms. 
     
     
       10. A compound of formula IV according to claim 1, wherein E is --COR 10  and R 10  is alkyl of 1 to 12 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl or phenylalkyl of 7 to 14 carbon atoms. 
     
     
       11. A compound of formula IV according to claim 1, wherein E is --COOR 11  or --SO 2  R 12  and R 11  and R 12  are each independently of the other alkyl of 1 to 8 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, aryl of 6 to 12 carbon atoms or phenyl alkyl of 7 to 14 carbon atoms. 
     
     
       12. A compound of formula IV according to claim 1, wherein R 1  is alkyl of 1 to 4 carbon atoms, alkyl of 2 or 3 carbon atoms substituted by one hydroxyl group, alkoxy of 1 to 12 carbon atoms, cycloalkoxy of 5 or 6 carbon atoms or alkanoyl of 1 to 4 carbon atoms. 
     
     
       13. A compound of formula IV according to claim 1, wherein R 1  is methyl, 2-hydroxyethyl, methoxy, heptyloxy, octyloxy, cyclohexyloxy, formyl or acetyl. 
     
     
       14. A compound of formula IV according to claim 1, wherein X is --O-- or --NR 2  -- where R 2  is hydrogen, butyl or dodecyl or a group of formula II. 
     
     
       15. A compound of formula IV according to claim 1, wherein X is --O--.